Benchtop ESR Spectrometer, Rare Earths, and Global Politics

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A company called Active Spectrum is marketing a benchtop ESR unit called the Micro-ESR that performs electron spin resonance measurements. The site says that the system operates at 3.4 and 9.6 GHz and has sub-micromolar sensitivity.  It’s pretty amazing, really.

I don’t know for a fact but the easy guess is that this ESR instrument and the picoSpin NMR spectrometer are based on some kind of rare earth magnet technology. Both instruments use very small cross section sample space, presumably to accomodate a design scheme to bring magnetic field lines together as closely as possible in the probe giving a useful field strength without a big electromagnet.

A quick patent search fails to turn up patents based on some obvious key words. I’ll have to spend some time looking more intently.

Now that I’ve got you hanging on to the rotating frame, lets tip you over with this.  China’s new policy of restricting rare earth element (REE) export as well as the recent announcement that it would be inposing fairly stiff tariffs means that wonders like these two magnet-based technologies are going to feel a pinch in raw material supply and competition real soon. The aggregate demand picture for REE’s will exceed supply by 2014 or so.  Market purists will nod knowingly and chant their homily on the rational allocation of goods by the market. 

But to what extent is China part of a rational market? China, Inc., really consists of a highly nationalized array of business fronts that are backed to the hilt by the Chinese government by internally favorable regulations on ownership and local sourcing. Don’t forget that Chinese currency is shielded from valuation excursions. 

To a large extent, China is leveraging technology developed in Japan and the west with metal resources highly concentrated within its borders to apply a pincer attack on the market place. China has industrial policy that it is steadfastly acting to strengthen its manufacturing base while the USA has an emphasis on aligning its citizens to be more receptive to consumption.

Wouldn’t it be nice to live in a country that tried harder to make its manufacturing industry more robust rather than the present fascination with finance and the well being of financiers?  Wouldn’t it be nice if westerners transferred a bit less of our magic to countries who will turn it into a stick to beat us over the head with? 

It is going to take a lot more than glib talk about the free market to deal with China and the growing influence of nationalized companies around the world.

New NMR on the Market: Non-Superconducting FT System.

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Check out the picoSpin website. This company is coming out with a 45 MHz permanent magnet NMR in 1Q2011 that produces FID’s so the user may collect FT spectra.  The instrument is somewhat larger than a toaster and is sensitive enough for many undergraduate and industrial applications. The customer must provide the computer and data workup software.

The other company out there offering non-superconducting FT systems is Anasazi Instruments. They have been refurbishing the fleet of 60 & 90 MHz CW systems sitting in storage rooms throughout academia into FT instruments.

I am jazzed. I think we might get one. OK. It is low field and low sensitivity. But that is often enough.  For an in-process check very often you’re just looking for one or two diagnostic peaks to collapse or grow to indicate reaction progress. This instrument could fit the bill.

I think many people will agree that the big supercon systems on the market, while well endowed with capability, often provide wildly more capacity than is actually used. A sort of creeping featurism.  This instrument is utterly utilitarian in conception and priced at $20,000.

I think this is a welcome addition to the selection of NMR instruments for the chemical field and I wish them well in their endeavors.

A willing suspension of belief. Anatomy of a liberal.

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I keep getting emails from conservative friends and acquaintances who are obsessed by what they call political correctness. In these emails, some kind of sarcastic parody is made regarding an alleged trend to ban the use of the phrase “Merry Christmas”.  Neoconservatives latch onto this like barnacles on the bottom of a tramp steamer. Inside their pointy heads they imagine that a cabal of liberals are scheming to take their guns and their religion from them.

If other liberals are like me (an admitted dissident), then not only do we not want to deprive them of  their damned firearms and bibles, but we want to put as many miles between us as possible. At least out of shooting range.

Christmas has a secular component and practice that even a bitter, crusty, non-religious liberal like myself can feel comfortable with. But as far as possible insensitivity to Jews and Muslims, well the decendents of Abraham will have to work that out amongst themselves.

In my limited sphere I don’t know of a single liberal who is trying to replace “Merry Christmas” with “Happy Holidays”. Only conservatives carp about this.  It’s a red herring promulgated by that famous yapping vaudevillian cur himself, Rush whatshisname, in the name of ratings.

——————

I’m moved to comment on what makes some people liberal.  A recent article in Slate was written by a conservative, Daniel Sarewitz, who seems to be genuinely perplexed at the apparent trend of scientists, or at least academics, to be liberal. It is though he is talking about a smallpox epidemic.  While I have no idea as to the C/L ratio of scientists and academics, I can say that from my perch on a small and obscure branch of the tree of science, liberals like myself are rather scarce.

Indeed, most of the industrial chemists I am in contact with are libertarians or evangelical conservatives or plain vanilla orthodox conservatives. So, from my limited data set,  Sarewitz’s complaint appears specious.

He probably refers to the life and eco-sciences, earth science, astronomy, big-time-physics, etc. I suspect that the balance is different in these fields.

But why would scientists trend towards a liberal viewpoint?  I have some ideas. First, the scientific approach to the world relies heavily on study and measurement.  Scientists tend to study analytically or, to use another term, critically. Critical study of the physical world requires a willing suspension of belief.  A scientist must keep a loose grip on beliefs because experimental results frequently force one to re-examine fundamental assumptions.  Fame and glory in science goes to those who tip over the apple cart of concepts with contrary results.  All scientists are excited at the prospect of looking at something in a new way.

I would offer that one attribute of a liberal person is the ability and willingness to reexamine ones fundamental assumptions. A corollary to this is that liberals are eager to acquire a new perspective on things in general. It is simply an artifact of curiosity.

Conservatives whom I know also appreciate study and measurement. But I think there is more of a trend towards devotional study rather than critical study. It’s about a greater knowledge of doctrine or greater fidelity with a catechism of policies.

Religionists upset with the notion of the separation of church and state often assert their right to be heard and to express their religiosity in public spaces.  Some liberals might take this as a simple matter of freedom of speech. And if that is all the religionists want, that would be fine. But if you look closely, they don’t want simple speech, they want to hold services in public spaces. They want to bring the civil sphere into alignment with their doctrine.

Religious services are about the veneration of the sacred. But “sacred” means that which is beyond question or understanding.  In a real sense, holding something sacred is to set apart a concept or doctrine from critical analysis. Religionists are not interested in a public critical analysis of their precepts. They are only interested in broader devotional covereage.

A liberal person is compelled to do critical analysis.  The very notion of sacredness is antithetical to one who seeks analytical truth. The policy that some concepts are beyond analysis is simply a form of thought control and is more suited to the Iron Age than the present.

For a good many people, college is a time and a place for intellectual experimentation and openness.  The university is an institution where critical analysis of the great world systems takes place.  The active examination of our world is the realm of the progressive.  Progressives push the boundaries of knowledge irrespective of where it might lead. Sometimes our analyses reflect well on our human or national institutions and sometimes it does not. But knowledge hidden is knowledge abused. That universities are loaded with liberals is a natural outcome of the shared intellectual adventure students are taking.

Merry Christmas from your liberal friend,

Th’ Gaussling

UN to Convene Special Pronunciation Session

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United Nations, New York, USA.  The United Nations has scheduled a special session on pronunciation aimed at the ultimate goal of harmonizing the pronunciation of Roman alphabet characters around the world.  Sir Angus MacGuiness, MP and Adjunct Undersecretary to Her Majesty’s Standing Council on Inflections and Pronunciation, has requested and required the British Delegation to the UN, via unanimous consent of Parliament, to petition for a special session on the subject of the pronunciation of the Roman alphabet.

Speaking for the office of the Adjunct Undersecretary, assistant Duncan Hiney Peebles disclosed to members of the press that the issue of how to pronounce words written in the Roman alphabet has gotten completely out of hand. “Between Polish, Welsh, and Icelandic, we have no idea even how to sound out these words” Peebles flatly stated. “We believe that the situation has gone completely bonkers and that an international body needs to convene on the matter.” 

When pressed on the matter of standarization, Peebles replied “naturally, we believe that British English should be the standard for pronunciation.  Minimally,” Peebles said, “words should be phonetically translated when printed in English speaking media.”

Peebles then went on to cite examples of words that should be phonetically translated even though they use Roman characters. “Take the case of the Islandic Volcano ‘Eyjafjallajökull’ ” Peebles pleaded. “For Christ’s sake!  It is pronounced eh eeya fyatla yokutla. How is anybody supposed to know to pronounce a double ‘ll’ as a ‘t’ sound? And then there is Polish and Welsh. This is insane and we have stop pretending that it is not a problem, ” Peebles pleaded.

A resolution been proposed and will come before the General Assembly in June of 2012, but is not expected to pass.

On Thermokinetic Safety

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So I’ve been working out a process for the last few days. Among other things the compound is a ketal and it’s synthesis is pretty simple. Ketone and diol brew in a pot of refluxing hydrocarbon and through the magic of equilibration, the water and hydrocarbon vapors condense and phase separate in a Dean-Stark apparatus. The water phase drops to the bottom of a graduated collector and the progress of the reaction is monitored by watching the water volume accumulate. 

This reaction is straight forward enough that I can easily make up the procedure myself. So I calculated a favorite weight percentage for concentration and pitched in the reagents. I chose a few of my favorite acid catalysts as well for a series of trial runs. Everybody knows that these reactions run faster with an acid catalyst. Such mechanisms are used to torment sophomore organic students everywhere.

After satisfactory completion with a few catalysts, I decided to round out my table of data with a run without catalyst. What better way to show the critical nature of the catalyst than to run a blank?

As luck would have it, the reaction ran splendidly without added catalyst. In fact, there was precious little increase in yield over the test interval with added catalyst.  Even better, without the catalyst the color of the reaction mixture was lighter (the substrate is a little sensitive).

So I took the carbonyl reagent and shook it up with some water and plunged a pH probe into it. What I had assumed to be a neutral organic material was quite acidic on contact with water. Hmmm.

A dive into the literature (patents, actually) revealed that the history of the compound most likely involves exposure to HCl from a continuous acid hydrolysis and steam distillation. And the Aldrich bottle did say that ca 1 % water is present. A fact that I neglected in my haste to set up the reaction.

The upshot is that I didn’t anticipate that there was residual acid catalyst in the reagent itself.

This is good to know from the scale-up perspective. An acid catalyst probably won’t be needed and loading procedures and sourcing do not have to be done to use a separate catalyst.  

Now the trick is to determine if it is safe to combine all of the reagents in the reactor or if one needs to be fed in as the reaction proceeds. A run where all of the reagents are in the pot from the start is called a batch run.  A run where one or more reagents are fed into the vessel over the course of the reaction is called a semi-batch run.  The reaction rate is greatest if all of the reagents are present from the start, but it does represent an accumulation of energy in a low phi-factor vessel that could be a runaway hazard. I’ll have to noodle through this issue if this reaction gets scaled up.

Taking into account the phi factor, or the thermal inertia of the system, is one of the crucial details in scale-up. Eventually, you have to make a decision on whether to configure the run as a batch or a semi-batch process. The precautionary principle usually leads to semi-batch unless you can prove that a batch configuration is safe.

Running a process at reflux with a heated jacket relies on the overhead condenser to be the primary thermal safety device. This usually is very effective in knocking down condensable components in the gas phase. A good condenser has a huge effect on the heat balance of a reactor system.

Knocking down condensable components helps to regulate the pressure and temperature of the pot. The transition from liquid to gas phase carries heat away from the reaction mass quite effectively under ordinary conditions.

However, it is possible for a reaction to accelerate to a point where the condenser capacity is inadequate. At such a point the jacket may be filled with heating fluid and a switchover to chiller fluid may take a relatively long time. 

A reactor can behave as an adiabatic system if you pick a time interval that is short enough. So, a reaction mass that exotherms rapidly enough may find itself in an approximately adiabatic containment. In this condition, the reaction mass can accelerate with gusto as pressure and temperature ramp skyward, multiplying the reaction rate. Decomposition reactions kick in and non-condensable gases are evolved that further pressure the system. Hopefully, the rupture disk and vent were properly sized because there is going to be an administrative mess to clean up afterwards.

This scenario is one to be avoided. Reaction calorimetry and ARC testing give results that help tremendously with engineering around a runaway scenario. A parameter of particular interest in the adiabatic Time to Maximum Rate (TMRad).  TMR is extracted from the slope of a linear portion of an Antoine curve determined by ARC. A formula for the line can be substituted with a desired time and a temperature can be calculated.

A particularly useful value to come from this is the temperature affording a 24 hour TMR. Many companies will determine the 24 hr TMR and set a policy to operate at a set temperature margin below the 24 hr TMR temp:  a 60 C margin is not uncommon.

American Plutocrats and Commoners

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It is really interesting how American commoners can support a political party that obviously serves interests of the top money earners and wealthy elites in this country. Perhaps they are waiting for some scraps to fall off the table? Or some of that lucre to dribble down their way in the form of a fabulous $9.00/hr retail job?   But, “commoners”?  What does that mean?

I figure that since the country seems bent on heading in the direction of a 19th Century-style society of stratified income classes, we may as well dust off the Victorian terminology and talk about how life is going to be. 

Power is the ability to allocate resources. As more and more resources come under the control of a wealthy minority, government seems to align itself increasingly to a small pool of influential and wealthy elite.  With the election of the upcoming congressional class, it is very clear that wealthy corporations and individuals are getting what they paid for-  statutory favors and influence in the deconstruction of the federal system of government. It is no coincidence that politicians from southern states, where an upswing in antebellum sentiment is afoot, are especially keen on the topic of states rights and other confederate sympathies.  Old antipathy is being dusted off and tried on for size.

Since SCOTUS has affirmed that money equals speech in Citizens United v Federal Election Commission, and that corporate funding of broadcasts cannot be limited under the First Amendment, anonymous streams of cash from conservative donors have flooded the 2010 election.  Such is the power of persuasion made by big money that a class of deconstructionists has been elected to the next session of congress.

Americans commoners have a fetish about the ways of the megawealthy.  Dial up CNBC sometime when Warren Buffett and Bill Gates are interviewed at one of the Ivy League B-Schools. Watch all of the gaga-eyed MBA students as they hang on every utterance proffered by these two American Plutocrats. It is a form of rapture. The students and faculty are under a kind of enchantment. But this is no different from the country at large. Watch how commoners behave around Donald Trump, or Oprah for that matter.

One of the things that will have to change in the near future is a rewrite of the local zoning codes pertaining to shanty towns and squatting.  As the population grows, as raw material scarcity increases, and as wealth continues to shift toward the wealthy side of the bell curve, more and more people will find themselves unable to house themselves. Increasingly we see a housing system heavily relying on credit and background checks, high rents, and the need to commute in America’s now balky system of suburbs.  The suburb system places a great distance between work centers and living centers, making transportation problematic for our up-and-coming dirt poor class.

As the population of dirt poor and destitute rises due to deindustrialization and dissolution of social safety nets (say, by 2030), all flexibility in the system will begin to play out and people will find themselves living in shanties and refrigerator boxes. They’ll become squatters. The local constables will have to deal with them because municipalities will refuse to compromise property values and will shun the homeless.

Let’s see.  What will the growing class of homeless do with their time? Write poems about the joys of laissez faire orthodoxy? I think that somebody will put together an appealing manifesto on insurrection.

Maybe our own village idiot, Glenn Beck, is right. Maybe there is a revolution underway. But I don’t think it is the one he is expecting.

Agricola Christmas

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I indulged in the purchase of a book I’ve had my eye on for a while. It is the English translation of De Re Metallica by Georgius Agricola, translated by Herbert Hoover and wife Lou Henry Hoover. This book (or collection of books) was published ca 1550. The English translation came out in 1912, written  by a young mining engineer from Iowa who would eventually become a US president. De Re Metallica is available in newly printed paperback form.

One issue that had stymied previous translators was the fact that Agricola wrote in Latin, a language that had been effectively dead for a thousand years, and Agricola needed vocabulary for situations that were not anticipated while the language was alive. So he invented vocabulary. Somehow the Hoovers were able to noodle  through this.  The translation is heavily footnoted.

Agricola was the first western scholar to document the mining arts as well as considerable geology and mineralogy. While I have not gotten too far with the book, it is apparent that mining technology in the European middle ages was fairly sophisticated by way of the mechanical contrivances used in the operations. Explosives would have been welcome then, but that was not to be for a long time.

They had milling machines, hoists, and sluices. They also performed cupellation, smelting, and calcining. Agricola discusses ore bodies, surveying, milling, property rights, and a host of other practical issues relating to oeprating a mine.

The book was published by a rare book publisher who performs print on demand (POD). There are a number of publishers who do this. Typically the copyright has fallen into the public domain.

Arsenic- Pnictogen of the Week

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The news of a bacterial life form that not only resists the toxic effects of arsenate but has been reported to use arsenate in place of phosphate has reverberated around the scientific world.  If the reported results are to be believed, then plainly this is a very significant find. (I haven’t been to the local library to read the Science article myself and I’m too cheap to pay for a download!)

From the reviews I have read, the paper reports the presence of the Group V oxoanion arsenate in the organism.  But the presence of an arsenate as a functional group in a biomolecule apparently has not been substantiated. I think this has to happen before we break out the champagne. Arsenate linkages have to be made in vivo by enzymes in order to qualify this as a new kind of life form.  It would be nice to hear about a successful enzymatic emplacement of arsenate in a controlled experiment. So far, all we know is that the organism is extremely tolerant of arsenate.

12/10/10. UPDATE.  My my my. Now we’re starting to hear doubters chiming in on the news of arsenious life forms at Mono Lake. What is that flushing sound?? Could it be the sound of careers circling ’round the porcelain bowl on the way to pergatory?  Remember Pons and Fleischman.

Extraordinary claims require extraordinary evidence.   C. Sagan

New play, new role

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Ended up with a part in our upcoming production of The Odd Couple. This one’ll be in a real theatre with an orchestra pit and a balcony.  I’m one of the card players. I get to be very ascerbic, which is something I can comfortably saddle up on. We have only 5 weeks ’til opening night so the pressure is back on. This play has a fair amount of physical comedy in it. And as before, we have some very experienced regional actors in it. And then there is me. I have to admit that it is more than a little intimidating.

Patent holiday

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It’s been days since I’ve shaved. I’ve spent 3 solid days over the Thanksgiving holiday hunkered down in my office studying patents and following threads through the IP swamps of Mordor.  A friend has engaged me to do some consulting and needs an IP map of a particular realm of industrial chemistry. I have no confidentiality overlap with this area of technology so I agreed. It sounded so easy when I said yes and estimated my fee. Now that I have blown well past anything I could ever hope to recover in terms of billable hours, I’m still blasting and hand shoveling muck from the pit of my own making.

His company is currently putting a plant in the ground to produce a well known commodity and the question foremost in their minds is- what added value beyond [—] does the product have?

I’m reasonably good at diving down the rabbit hole in the patent world and finding what I need to know. But the current project has forced me to press into use more USPTO resources since I don’t have a personal SciFinder account for this work. Especially useful has been the classification system.  Patent lawyers will scoff at my swoon over this and flash their Esquire stinkeye since they are all too familiar with it. But chances are they don’t use SciFinder like chemists do.

SciFinder’s ability to find patent families from a structure or CASRN input is phenomenal. Even from within Markush claims.   I’ve had one search with combined SciFinder/USPTO resources compared with legal specialists using their own search tools. My search was just as exhaustive as theirs. Yes, SciFinder has flaws. And not finding claims is like a negative experiment.  But it is a very good tool for combing the ground.

Part of my approach stems from my natural inclination to browse. I drive people nuts when I go to a store with them because I will thoroughly examine the contents of the store for interesting items.  I drive the merchants nuts because my browsing rarely results in a sale.  (Notice that the theme is that I drive people nuts.)

Once you find a lead patent it is important to search the classification as well as cited patents. It is a simple matter to do a search by classification and dredge up hits. Once the fish are on board, it is about sorting the results and casting the trash fish back in the water. 

Google Patents is an excellent resource and I heartily recommend it. It retrieves pdf’s of the entire patent document as well as providing links to patents cited and those patents citing the patent of interest. It also links to the the classification site at the USPTO. A simple click of the mouse in the USPTO site pulls up a search of all of the patents under that classification.

On occasion, Google patents will not retrieve a particular patent or application. This seems to happen with very newly issued patents and applications in general. For this circumstance I use pat2pdf.org.  You might have to monkey with the formatting of the application number string, but it almost always returns the document eventually.

OK. It’s fine to be able to retrieve a bunch of patent numbers and pdf’s. But soon one becomes overwhelmed by the large amount of highly dense data that has been recovered.  In my surveys, I use a form meant to collect key information, but sized in a manner so as to limit the amount of detail I can write down. Feel free to use this form or modify it as you please.

Patent Summary Blank Form

At some point it becomes useful to use Excel to develop a matrix of patent information. In particular, one can retrieve a list of patents from the PTO and cut and paste them into Excel. They’ll paste as hotlinks, so all you have to do is to right click on the cell and select the unlink option. Tedious but effective.

I have developed an Access database to store patent information and other IP office actions and produce reports for due diligence studies. This is very handy, but eventually you become enslaved by upkeep as is true with all database tools.

Am I suggesting that one does his own lawyering? Not at all.  But if you’re in high tech manufacturing, one must be very careful to avoid infringement. It it crucial that a few technical people in the organization be familiar with the patent picture.  It is far better to avoid infringement in the first place than to have to find a way out of it.

The best way to use a patent attorney is to be informed in all interactions with them.  While they can often noodle through a problem presented to them by napkin scribblings and hand waving, it is best for the client to be knowledgeable about the patent landscape and to help the attorney to focus on the key legal issues. Good lawyering happens when the attorney clearly understands the nuances of the problem and can act accordingly. Having a list of prior art or other IP facts will save you billable hours in the form of research and needless office actions.

Your attorney is an officer of the court and has a legal obligation to honesty and fidelity to the system.  Being well informed in advance and working cooperatively with a patent attorney will go a long way to staying out of litigation.

The other good reason for closely studying the patent literature is to find what some call the “white space”.  This is the negative space around the claimed art that is not claimed and is likely to be free to practice or fertile enough to file a application on. If you Google “patent white space” you’ll find that this is a cottage industry.  A study of white space may provide insight into maneuvering room around a patent.